Dyeing of nylon and acetate silk in



Patented Aug. 18, 1953 DYEING F NYLON AND ACETATE SILK IN SITU WITH ICECOLORS Clemens Streak, Loudonville, N. Y., assignor to General Aniline &Film Corporation, New York, N. Y., a corporation of Delaware No Drawing.Application February 23, 1950, Serial No. 145,715

8 Claims. 1

The present invention relates to an improvement in the dyeing of nylonand acetate rayon by impregnating the fibers with an ice-color couplingcomponent and an amine base in the presence of a guanidine compound, andsubsequently forming azo dyes therefrom on the fiber.

It has been proposed to dye nylon or acetate rayon fibers byimpregnating the fibers with an alkali metal salt, 1. e., sodium salt ofan ice-color coupling component and an amine base and subsequentlydiazotizing the base and coupling the same with the ice-color couplingcomponent. The dyeings obtained in this way, however, are of littlecommercial value, being weak, off-shade dyeings of poor fastnessproperties.

The inability of the art to obtain satisfactory dyeings by the aboveprocedure is attributable (l) to the very low affinity of the fibers forthe salt of the ice-color coupling component, (2) to the considerabledecomposition ofthe diazonium compound which occurs before formation ofthe color in the fiber takes place, and (3) to incomplete coupling ofthe salt of the ice-color coupling component and the diazom'um compound.

Attempts had been made to eliminate these objections by employingswelling agents, such as alcohol, Cellosolve, thiocyanates and thioureain an effort to increase the afiinity of the fibers for the dyecomponents. The improvement attained in this way is at best minor and ismore than oifset by the increase in cost resulting from the use of therather expensive agents involved. As a matter of fact, the status at thepresent time of nylon dyeing by means of an ice-color coupling componentand an amine base is rather precisely stated by the following extractfrom page 748 of the issue of October 17, 1949, of American DyestufiReporter: The Naphthol dyes can be applied with the prepare and base inone bath and subsequently be diazotized and developed in one operationin a second bath. However, we have not succeeded in obtaining on nylonthe bright shades obtained on cotton, nor have we obtained the light andcrocking fastness that is required. Work is being continued to obtainthe desirable properties of the Naphthol dyes on nylon.

It has now been discovered that the aforementioned method may beutilized in connection with nylon or acetate rayon fibers whileobtaining dyeings having a satisfactory depth of shade and brightnessand excellent fastness properties by effecting the impregnation of thefibers in the presence of a guanidine compound. The

guanidine compound operates in a poly functional manner in insuring theformation of excellent dyeings. Thus, it increases the affinity of thefibers for the coupling component by converting the ice color couplingcomponent into a salt which is more strongly attracted by the fibersthan the coupling component per se or its sodium salt. The couplingcomponentguanidine salt imparts greater stability to the diazom'umcompound than the corresponding sodium salt. Finally, it effects abuffer efiect leading to more even and brilliant dyeings.

The dyeing of nylon and acetate rayon fibers with an ice color byimpregnating the fibers with an ice color coupling component and anamine base while insuring the presence of a guanidine compound duringsuch impregnation, salts of guanidine compounds with ice color couplingcomponents, and impregnating compositions containing a guanidinecompound and one or both of the aforesaid dye components constitute thepurposes and objects of the present invention.

The amine base employed may be any aromatic primary amine useful in thepreparation of azo dyes. Examples of such amines are:

4-nitro-o-anisidine 2,5-dichloro aniline i-benzoylamido-2,5-diethoxyaniline 2-amino-4,4-dichlor-diphenyl oxide Amino azo toluene5-methyl-o-anisidine m-Chlor aniline o-Chlor aniline 4-nitro-o-toluidine4-amino-S-benzoylamino-m-xylene Tolidine 1 3-amino carbazole Amino azobenzene 4-chloro-o-toluidine a-Naphthylamine4-amino-4-dihydroxyethylaminoazobenzene 4-chloro-2-m'tro aniline4,4'-diamino diphenylamine l-amino-anthraquinone N- (p-aminobenzoyl)-p-toluidine, and the like.

Such compounds, as is well known, are typical ice-color bases.

The coupling component to be utilized in forming the azo dye is any ofthe well knownicecolor coupling components. Examples of such compoundsare the following Naphthol AS type compounds:

,8Hydroxy naphthoic-p-chloranilide cally mixed and the mixture dissolvedand ap plied to the fibers. Finally, the guanidine compound and the icecolor coupling component may be reacted to form a salt and the salt andthe amine base may be dissolved and appliedto the fibers. Irrespectiveof the particular mechanical method utilized in bringing the componentson the fiber, the net result is invariably the same, to wit, dyeings areobtained 3-hydroxydiphenyleneoxide2 carboxylic amine3-hydroxydiphenyleneoxide 2 carboxylic acid anisidide9-methyl-2-hydroxycarb'azole 3- carboxylic acid anilid'e9-methyl-2-hydroxycarbazole-3-carboxylic acid anisidi'de9-methyl-2hydroxycarbazole-3-carboxylic acid toluidide 3-hydroxyfluorene-Z-carboxylic acid o-toluidide,

and .the like.

Guanidine' compounds which I have found to be effective for my purposeare those of the following formulae:

wherein R1 and R2 are hydrogen, alkyl such as methyl, ethyl, propyl,butyl, octyl, decyl and the like, aryl such as phenyl, naphthyl, tolyl,ethylphenyl and the like, aralkyl such as b'enzyl, 'menaphthyl and thelike, cycloaliphatic such as cyclopentyl, cyclohexyl and the like, and.the salts of such compounds, .suc'h, as carbonate, hydrochloride,nitrate, sulfate, phosphate and acetate. Illustrative examples of suchcompounds are guanidine, guanidine carbonate, guanidine hydrochloride,guanidine sulfate, guanidine nitrate, guanidine acetate, guanidine,phosphate, amino guanidine, amino guanidine bicarbonate, aminoguanidine'. hydrochloride, amino guanidine sulfate, B-diphenylbiguanide, B-diphenylbiguane ide hydrochloride, methyl guanide, ethylguan ide, propyl guanide, phenyl guanide, N,N-diphenyl guanide, benzylguanide, B-dibenzylbiguanide, biguanide hydrochloride, phenyl biguanidehydrochloride, methyl biguanide, ethyl biguanide hydrochloridaand thelike.

The effect desired .byutilization of th e guanidine compound may berealized in a numberof ways. For instancathe amine base andthe guanidinecompound may be dissolved, the ice color coupling component added to thesolution and th solution applied to the fibers; or the ice colorcoupling component and the 'guanidine compound may be mech'ar'iicallymixed and the mixture dissolved along with the amine base whereupon the.solution is applied to the fibers;

or the ice color coupling component, amine whilerealizing the particularadvantages previ'ou'sly discussed.

For impregnation of the fibers, the components are applied thereto inthe form of an aqueous solution. A smallamount of a water miscibleorganic solvent suchas ethanol, butanol, Cellosolve,- benzyl alcohol,ethylene glycol, and the like,

added t'o assist dissolution of the components if desired. Preferably asmall amount of aZ-W-etting agent is included in the impregnation bathand for this purpose there may be employed, inter alia, oleyl methyltaurine, the addition product of diisobutyl phenol with '8 to 10 molecules of ethylene oxide, th sulfonated' condensation product of benzenewith keryl chloride (i. 'e.-, chlorinated kerosene), di-isobutylnaphthalene sulfonate, the product sold under the trademark Tamol NNO (aproduct produced by condensing, Z-naphthalene-sulfo-nic acid withformaldehyde), and the like.

The quantities of various dye components and guanidine compound employedmay vary to a considerable extent. Usually, equivalent quantities ofamine base and coupling component may be used but in practice it hasbeen found that better results ensue when employing a slight excess ofthe coupling component.

The in'fiuence of the guanidine compound is-felt even when traces areadded to the impregnation bath. It is recommended, however, that thequantity of the guanidine compound range from 1% to 5% by weight ofthematerial to 'be dyed.

When the guanidi-ne compound is used in the form of a salt, it isdesirable to include an alkali in the impregnation bath. For thispurpose, there is preferably used a small'amount of astron-g'inorganicor organic'base, such as caustic soda,-potassium,hydroxide, caustic potash, ethylene diamine, tetraethylene pentamine, orthe'like.

After the impregnation of the fibers with the guanidine compound and thedye components, the fabric is subjected to the action of a'diazotization bath containing sodiumnitrite and an acid such assulfuric, hydrochloric, acetic, formic, or the like. The temperature ofthe bathmay vary from room temperature tothe boil'for about i to 45minutes to permit dyeformationto take place. The materialis then rinsedand finished in the usual manner.

It has been s'tatedabove' that one of thee-ffects 0f the guanidinecompound is-the'conversion of the ice color coupling componentinto'the'salt thereof, either in whole ;or impart, depending upon thequantities of the ice color coupling component and guani'dine compoundemployed; It has also been stated that salt formation may beeffectedprior to the application of the components to the fibers. Wherethe saltis not preformed, it is consideredthatsalt formation inevitablytakes place during dyeing of the fibers With the compositionscontaining-theguanidine compound.

7 Various tests have ibeen made forthe purpose of establishing that'saltformation actually results when treating various ice color coupling comne s. wi eua idine com-pounds. 'Thus,

2.97 g. of c-hydroxynaphtholic acid p-chloroanilide and 2.73 g. ofB-diphenylbiguanide were mixed with sufficient alcohol until a yellowcolored uniform paste resulted. The paste is dried at 50 C. under vacuumand then milled to a fine powder. The light tan powder, i. e., thep-diphenylbiguanide salt of p-hydroxy-naphthoic acid p-chloroanilide,has a melting point of 137- 143 C. and is soluble in alcohol andCellosolve forming greenish yellow solutions.

The corresponding c-hydroxynaphthoic acid p-chloroanilide is practicallyinsoluble in these solvents and has a much higher melting point, to Wit,262.5-263C.

The corresponding sodium salt has a high degree of solubility in theaforementioned solvents but does not have an exact melting point,decomposition setting in before melting occurs.

No caustic soda is present in any case, so that the sodium salt couldnot possibly have been responsible for the melting point determinationwhich was made.

3.37 g. of 2-hydroxy-3-carbazoleca1 boxylic acid p-chloroanilide, .955g. of guanidine hydrochloide and .4 g. of dry caustic soda are mixedwell with sufficient alcohol to form a paste, dried at 50 C. under avacuum and then milled to a fine powder. The light tan powder has amelting point of 219-224 C. and is soluble in alcohol and Cellosolve toa high degree.

The corresponding 2-hydroxy-3-carbazolecarboxylic acid p-chloroanilideis practically insoluble in the above solvents and has a melting pointof 258.5-259.5 C. Salt formation accordingly occurred also in thisinstance.

3.13 g. of ,B-hydroxynaphthoic acid a-naphthanilide, 2.14 g. ofphenylbiguanide hydrochloride and .4 g. of dry caustic soda are mixed ina1- cohol, dried and pulverized. The greenish yellow powder is solubleto a high degree in alcohol and Cellosolve and has a melting point of165- 168 C.

The corresponding p-hydroxynaphthoic acid a-naphthanilide, on the otherhand, is practically insoluble in the above solvents and has a meltingpoint of 220-221 C.

The sodium salts of 2-hydroxy-3--carbazolecarboxylic acidp-chloroanilide and of fi-hydroxynaphthoic acid a-naphthanilide meltwith decomposition. It is known that this is a pecularity of sodiumsalts of the type of compounds under discussion.

.6575 g. of ,B-hydroxynaphthoic acid anilide were dissolved in 200 ml.of methyl alcohol C. P. To the solution there were added .46 g. ofguanidine carbonate dissolved in about ml. of distilled water. Thissolution in turn was added to .6575 g. of the above B-hydroxynaphthoicacid anilide which was dissolved completely in 600 ml. of methylalcohol. The methyl alcohol was then distilled oil.

The X-ray diffraction pattern of the crystalline product thus obtainedwas compared with the X-ray diffraction pattern of a sample of ,3-hydroxynaphthoic acid anilide, on the one hand, and of guanidinecarbonate on the other hand.

The diffraction patterns were obtained by permitting a narrow pencilradiation to penetrate a thin sample of each of the compounds underinvestigation. The X-ray beam itself is trapped in a small lead cup. Thediffraction effects which arise from the sample are then recorded on acurved film wrapped in black paper.

It has been found over a period of many years 6 that these X-raydifiracti'on effects from crystalline materials are very characteristicand can be used as "finger prints for the identification of suchmaterials.

The result of the X-ray diffraction pattern performed on the salt ofguanidine carbonate and the beta-hydroxynaphthoic acid anilide shows adiffraction pattern differing entirely from the pattern obtained fromguanidine carbonate on the one hand and of the beta-hydroxynaphthoicacid anilide on the other hand. The: patterns of the latter twocompounds are completely absent in the pattern obtained from the salt ofguanidine carbonate and the beta-hy droxy-naphthoic acid anilide,clearly indicating. therefore that the latter mentioned compoundcorresponds to a new crystalline state of matter resulting from theformation of a compound suificiently stable to be isolated.

The afcrestated tests, performed with different ice color couplingcomponents and guanidine compounds, are considered to establish theconclusion that the guanidine compound forms a salt with the ice colorcoupling component, thus providing an explanation as to why theguanidine compound operates as it does to yield intense even dyeings bythe amine base-ice color coupling component method.

The invention is further illustrated by the following examples, althoughit is to be understood that these examples are not limitative.

Example I .1 gram of 4-benzoylamido2,5-diethoxyaniline, .110 gram ofp-hydroxy-naphthoic-p-ch1oroanilide, .01 gram of oleyl methyl-taurineand .3 gram of guanidine carbonate are dissolved in 1 cc. of Cellosolve,1.5 cc. of hot water and .25 cc. of 40 B caustic soda. The mixture isheated gently and diluted to the desired dilution (as an example, 200cc. of warm water are added). A sample of nylon weighing 10 grams istreated in the above bath for 45 minutes at 6065 C. followed by rinsing.The material is then transferfed to a bath containing 5% sodium nitrite(based on the weight of material) and 10% acetic acid (based on theweight of material) and maintained in the bath for 20 minutes at 60-65C. The material is rinsed and finished in the usual manner.

A bright greenish blue coloration is obtained on the nylon, muchstronger and brighter than in a sample dyed in similar manner withoutthe addition of the guanidine carbonate.

Example II The procedure of Example I Was repeated While utilizingacetate rayon in lieu of nylon. The dyeings obtained on the acttaterayon were comparable to those obtained on the nylon.

Example III Example IV .1 gram of 2 amino-4,4-dichlorodiphenyloxide, .13gram of p hydroxy-napthoic-1-naph-- .1. grain of2-aniinoeAf-dichlorodiphenyloxide, .175 gramof: -benzoyla:ce.tamido -2:,5 -di'- methoxybenzanilide,,.0l gram of oleylmethyltanrine and..3 gramof gnanidineg-carbonate are dissolved and employed. todyanylonasinExample IV. A very strong golden. yellow shade is obtained onthe nylonwhichzis remarkablybrighterthan thatobtained ii the. guanidinecarbonate. is excluded. A sample oiacetate rayon gives similar results.

Example VI .1 gram of aminoazotoluene. .15 gram-offl-hydroxy-naphthoic-Znaphthylamide, .01 gram of oleylmethyltaurine and.3 gram ofguanidine carbonate are disolved' and dyed on nylon andacetate rayon as in Example IV. A very bright.

maroon shade is obtained inboth casesand the shade is muchstrongerandbrighter in the presence of the guanidine carbonate than in asimilar; dyeing which excludes the guanidine carbonate;

Example VII' .1 gram. of: aminoazotoluene, .185 gram of 2- hydroxy llbenzo; (a) carbazole 3 carboxylic-p-aniside. .01: grant ofoleyl-methyltaurine. and .3 era-moi guani'dine carbonate are dissolved;and-:- employed to. dye nylon and ace- 'tate. rayon asin Example IV.Strong, deep black shades are; obtained when guanidine carbonate ispresent Which contrast greatly to the dull grayish blaclc shadesobtained when guanidine carbonate is excluded.

Example VIII .05 gram of 5-methyl-o-anisidine, .11 gram of,c-hydroxy-naphthcic-m-nitroanalide, .01 gram of oleylmethyltaurine and.3; gram of" amidoguanidine bicarbonate are dissolved as in Example I. Agram sampl of, nylon is impregnated as in Example I and then developedin a bath containing 5% sodium nitrite and 5% sulfuric acid for 10minutes at 60-65 C. The. bathis neutralized with 7% ammonia. (based onthe weight of material) and the color is allowed to develop for another10. minutes. The sample is rinsed and finished as usual. A bright,strong bordeaux shade is obtained on both nylon and acetate rayon whichcontrasts greatly to similar dyeings excluding the guanid-ine compound.

Example IX The procedure is the same as in Example I excepting that theguanidine carbonate is replaced by .3 gram of amido guanidinebicarbonate. The dyeings obtained. were quite similar to those ofExample I.

Eaiample X ..1 gram of. 5-methyl-o-anisidine, .22 gram of 5 chloro 2 ,4dimethoxy acetoacetanilide, .01

gram. 1 of oleylmethyltaurine and? .3 gram of guanidine carbonate aredissolved and dyed as-in Example I. A bright greenish yellow dyeingresuits. on bothnylon and acetate fibers. Without the addition ofguanidine carbonate, the shade is reddish, dull and weak.

Example XI .l' gram of 2'-amino-4,l-dichlorodiphenyl oxide, .08 gram ofphenyl methyl pyrazolone, .01 gram of oleylrnethyltaurine and .3 gram ofguanidine carbonate are dissolved and employed to dye nylon and acetatefibers as in Example IV. A yellowish shade is obtained which isnoticeably stronger than. similar dyeings made without guanidinecarbonate.

Example XII The procedure is the same as in Example I excepting that theguanidine carbonate is re placed by .3 gram of guanidine hydrochloride.The results are substantially the same.

Example XIII The procedure is the same as in Example I excepting. thatthe guanidine carbonate is replaced by guanidine sulfate. The dyeingsresulting' are excellent.

Example XIV .66 gram of 4-benzoylamido-2,5-diethoxyaniline, .05 gram offi-hydroxy-naphthoic anilide and .3 gram of p-diphenylbiguanide aredissolved in 2 cc. of Cellosolve. This solution is poured into 200' cc.of warm water containing .025 grain of oleylmethyltaurine.

A 10 gram sample of nylon is dyed in this solution at 65 -C. for 45minutes, then rinsed and developedin a fresh bath of 5% sodium nitriteand. 10% acetic acid for 20 minutes at Gil-65 G. The dyeings are rinsedand finished as usual. Deep blue. dyeings are obtained on the nylon alsoon acetate rayon when treated as above. Dyeings without the pdiphenylbiguanide are dull and weak.

Example XV The procedure is the same as. in Example XIV excepting thatthe ,B-diphenyl biguanide is replaced by guanidine. The results aresubstantially the same as those of Example XIV.

Example XVI Eaample XV'I I I .06 gram ofl-benzoylamido-lEa-diethoxyaniline; .05 gram of ,B-hydroxy-naphthoicanilide and .3 gram of B-ciiphenylbigUanide are dissolved in 2cc.of'Cell'osolve and .25 cc. of caustic 49 B. This solution'is pouredinto 200cc. of warm water containing- .25 gram of oleyl methyl taurine.

Bright deep blue; dyeings. are obtained on nylon and'acetate rayon as inExample Example XIX' ..1 gram 0f. -zeamino lA -dichlor.odiphenyl oxide,.13 gram of fl-hydroxy-naphthoic-lnaphthylamide, .01 gram of oleylmethyl taurine and .3 gram of phenyl biguanide are dissolved as inExample I. Dyeing is as in Example IV and results are similar.

Example XX Example XXI .1 gram of the compound of the formula:

C2HiOH .11 gram of S-hydroxy-naphthoic-p-chloroanilide, .01 gram ofoleyl methyl taurine and .3 gram of guanidine carbonate are dissolved asin Example 1. Nylon and acetate rayon are dyed and developed as inExample IV. A deep black shade is obtained on either fiber.

Example XXII .1 gram of oxide, .13 gram of,B-hydroxy-naphthoic-l-naphthylamide, .01 gram of oleyl methyl taurineand .3 gram of biguanide are dissolved as in Example XIX. Results aresimilar to Example XIX.

Example XXIII .1 gram of 2-amino-4,4'-dichlorodiphenyl oxide, .13 gramof ,B-hydroxy-naphthoic-l-naphthylamide, .01 gram of oleyl methyltaurine and .3 gram of biguanide hydrochloride are dissolved as inExample XIX. Results are similar to Example XIX.

Example XXIV 2.97 g. of ,B-hydroxynaphthoic acidp-chloroanilide and 2.73g. of fl-diphenylbiguanide are mixed well with sufficient alcohol untila yellow colored uniform paste is obtained. The paste is dried at 50 C.under vacuum and then milled to a fine powder. The light tan powder isthe fi-diphenylbiguanide salt .of p-hydroxynaphthoic :acidp-chloroanilide. It has a M. P. of 137-143" C. and is soluble in alcoholand Cellosolve forming greenish yellow solutions.

.220 g. of this product and .075 g. of 2-amino- 4,4-dichlorodiphenyloxide are dissolved in 1 cc. of Cellosolve and .25 cc. of caustic soda40 Be. This is combined with 200 cc. of warm water containing .1 g. of"Tamol NNO. A 10 g. sample of nylon is impregnated with this solutionfor 45 min. at a temperature of 60 C. and developed with 5% sodiumnitrite and 5% sulfuric acid for 20-30 min. at a temperatuer of 60 C.The dyeings are rinsed and dried as usual, giving a strong red shade. Indyeing acetate rayon, it is preferred to replace the sulfuric acid ofthe developing bath by acetic acid.

Example XXV 3.27 g. of fi-hydroxyanthroic acid o-toluidide, 1.35 g. ofaminoguanidine bicarbonate and .40 g. of dry caustic soda are mixed wellwith sufficient alcohol to form a paste. The paste is dried at 50 C.under vacuum and milled to a fine brick red powder which is soluble inalcohol and Cellosolve and ha .3 M- B Somewhat a ove 360 C.

2-amino-4,4-dichlorodiphenyl 10 .160 g. of the above product and .080 g.of 4-amino-2,5-diethoxy-benzanilide are dissolved in 1 cc. of Cellosolveand .25 cc. of caustic soda 40 B. This solution is poured into 200 cc.of warm water containing .100 g. of Tamol NNO. A10 g. sample of acetaterayon is impregnated with this solution for 45 min. at 60 C., rinsed anddeveloped with 5% sodium nitrite and 30% acetic acid (28 B.) for 20 to30 min. at 60 C. The dyeing is rinsed and finished as usual, giving astrong green shade.

Similar results are obtained when dyeing nylon in place of acetaterayon.

Example XXVI 3.13 g. of B-hydroxynaphthoic acid-a-naphthanilide, 2.14.-g. of phenylbiguanide hydrochloride and .40 g. of dry caustic soda aremixed in alcohol, dried and pulverized. The greenish yellow powder issoluble in alcohol and Cellosolve and has a M. P. of 165 to 168 C.

.180 g. of the above powder and .075 g. of'2-amino-4,4'-dichloro-diphenyl oxide are dissolved as in Example XXIV.Dyeings on nylon and acetate are obtained as in Example XXIV, thecoloration being a bright bluish red shade.

Example XX VIII 3.0 g. of s-hydroxynaphthoic acid-2-naphthy1- amide, 2g. of guanidine carbonate, 2 g. of Tamcl NNO and .44 g. of caustic sodaare mixed and pasted well with water in a mixer at about C. It was driedat 90 C. in a vacuum. The greenish yellow material is soluble in alcoholand Cellosolve.

.25 g. of the above product and. .10 g. of4-amino-2,5-diethoxy-benzanilide are dissolved as in'Example XXV anddyeings made as in Example XXV. A deep greenish blue shade is obtainedon nylon and acetate rayon.

Example XXIX 1 g. of 4-amino-2,5-diethoxybenzanilide, 1.1 g. offl-hydroXy-naphthoic acid p-chloroanilide and 1.0 g. of guanidinecarbonate are mixed together and pulverized into a fine powder.

.31 g. of this mixture are dissolved in .50 cc. of Cellosolve and .25cc. of caustic soda 40 B. This is diluted with 200 cc. of warm watercontaining oleyl methyltaurine. A 10 g. sample of nylon or acetate rayonis impregnated with this solution and developed as in Example I withsimilar results.

Example XXX 1.30 g. of ,c-hydroxynaphthoic acid l-naphthylamide and 1.00g. of ,B-diphenylbiguanide are mixed and ground to a fine uniformpowder.

.23 g. of the above mixture, .1 g. of 2-amino- 4,4-dichloro-diphenyloxide and .01 g. of oleyl methyltaurine are dissolved as in Example IV.V

11 Bright bluish red shades are obtained on nylon and acetate rayon whendyed as in Example IV.

Example XXXI 1.0g. of aminoazotoluene and 1.0 g. of guanidine carbonateare mixed and ground to a fine, uniform powder.

.20 gram of the above powder, .15 g. of ,B-hydroxynaphthoicacid-Z-naphthylamide and .01 g. of oleyl methyltaurine are dissolved anddeveloped as in Example III. Very strong, bright maroon shades areobtained.

Example XXXII .075 g. of 2-amino-4,4'-dichlorodiphenyl oxide, .10 g. ofB-hydroxy-naphthoic acid p-chloroanilide and. .40 g. of guanidinecarbonate are combined with 1- cc. of Cellosolve. The mixture is gentlyheated and the yellowish colored solution is poured into 200 cc. of warmwater containing. .03 g. of oleyl methyltaurine. The solution hasa milkyappearance.

A 10 g. sample of nylon is impregnated in this bath for 45 min. at 60 C.During impregnation the nylon yarn takes on a deep greenish yellowcoloration and the fi-hydroxynaphthoic acid-p-chloranilide is completelyexhausted from the bath. The greenish yellow colorationof the nylonfiber is due to the formation on the fiber of the guanidine salt of theB-hydroxynaphthoic acid-p-chloranilide.

The sample is then developed by treatn'ient with sodium nitrite and 5%sulfuric acid for 30 min. at 60 C., rinsed and finished as usual. Astrong, bright red coloration results.

Example XXXIIL .08 g. of 4-amino-2,5-diethoxybenzanilide, .075" g. ofS-hydro'xyhaphthoic acid anilideand .300 g. of guanidine carbonate aredissolved with 1 cc. of Cellosolve. The mixture is heated gentl and thenpoured into- 20000. ofwarm water containing .020 g. of oleylmethyltaurine. A greenish y'ellovv solution is formed.

A g. nylon sample is impregnated with'thi's' greenish-solution for 45min. at 60 C. and thenrinsed; The nylon takes ona deep yellow colorationand the coupling component is practically completely exhausted.

The dyeing is developed by treatment with 5% sodium nitrite and 10%acetic acid for min. at 60 C. The sample is rinsed and finished asusual.A very strong blue dyeing is obtained.

Example XXXI V .10 g. of 4-amino-2,5-diethoxybenzanilide and .09 g. ofp-hydroxy-naphthoic acid anilide are dissolved with 1 cc. of Cellosolveand .25 cc. of caustic soda- This solution" is poured intoan alreadyprepared solution containing-200 cc. of water, .01 g. of oleylm'ethyltaurid'e' and" .20'-g. of guanidine carbonate.

10 g. ofnylo'n are impregnated in thisfsolution for min. at 60 C., thenrinsed andldeveloped" with 5% sodium nitrite and 30% acetic. acid' (28Bi) for 30min. at 60 C. The dyeing is rinsed: and finished as usual,yielding a strong blueshade. A sample treated in similar manner withoutthe addition of the guanidine salt is very weak in color.

Example XXXV g; of B-hydroxynaphthoic acid. anilideand 50 g. ofguanidine carbonate are pasted. up with alcohol on a steam bath. Duringthis operation the alcohol evaporates off, leaving as residue a yellowstubstance which is solubleiii-col a e caustic soda (40 Be).

This product differs from a mechanical mixture of s-hydr'oxy naphthoicacid anilide and guanidinecarbonate which is not yellow in color andwhich dissolves in water only when heat is applied to form a yellowsolution.

In both cases equally strong dyeings are obtained on developing with adiazonium compound of any of the preceding examples.

Example XXXVI 50 g'. of B hydroxynaphthoic-p-ch1oranilide and 50 g. ofguanidinecarbonate are treated as in Example A mechanical mixture ofthesame coupling compound and guanidine carbonate give dyeings which are asstrong as those produced with the above compound.

Example XXXVII 50 g. of fi -hydrox-yn'aphthoic-2-naphthylamide and 50g". of guanidine carbonate are mixed to gether under the same conditionsas in Example XXXV. A yellow" pulverulent substance results whichexhibits dyeing properties equivalent to those of a mechanical mixtureof the coupling component and-guanidine carbonate.

ExampleXXXl HI 50 g. of B-hydroxy'anthroic-o-toluidide are pasted upwith alcohol on' a steam bath as in Example While heating the mixture,the yellowish color of the toluidide gradually changes to a' reddishbrown, thus indicating a chemical reaction. The product exhibits aboutequal dyeing properties when dyed against a mechanical mixture of theaforesaidtol uidide and guanidine carbonate. a

50 g; of ,e-hy'droxy'nap'hthoi'c acid anilide and 50" g. of guanidinecarbonate are mechanically m'ixedby grinding't'ogether'. An almostcolorless mixture results which exhibits dyeing properties that are on apar'witli the' compound of Example The following indicate how guanidinecompounds affect the exhau'stof ice color coupling components on nylon.

.10 g. or B-hydroxynaplithoic acid-m-nitroanili'd'e were dissolved with1 cc. of Cellosolve and. A1. cc. of caustic soda (40 Bel). This solutionwas diluted with 150 cc. of warm water containing. .10 g. of Tamol NNO'.

10 g". of nylon ya'rn' were steeped-in this bath at C. for 45 mina-n'dthen-rinsed. At this point the impregnating bath, on testing with aspectrophotometer, indicated that 60.6% of the c-hydroxynaphthoi'c acidm nitroanilide was taken up by the fiber and" 30.4% remained in thebath.

.10 g; of B hydroxynaphtho'i'c acid-m-nitroanilide and .20 g. of'guanidine carbonate were dissol'vedwith 1 cc. of Cellosolve and A; cc.of

with cc; orwa'rmwa'ter containing .10 g. of Tamol NNO.

10 g. of nylon yarn were steeped in this bath as above. Theimpregnating; bath, on testing with a spectrophotometer indicated that92.7%

This solution was diluted Example X LI .075 g. of p-hydroxynaphthoicanilide and .08 g. of 4-benzamido-2,5-diethoxy-aniline were dissolved in1 cc. of Cellosolve and 4 cc. of caustic soda (40 B.). This was dilutedwith 150 cc. of warm water containing .10 g. of Tamol NNO.

10 g. of nylon yarn were dyed for 45 min. at 60 C. and then rinsed anddeveloped with 5% sodium nitrite (based on the weight of the nylon) andacetic acid in 150 cc. of water for 30 min. at 60 C.

The dyebath was tested by spectrophotometer as in Example XL, which testindicated that 43.7% of the B-hydroxynaphthoic acid anilide had beentaken up by the fiber and 56.3% remained in the dyebath.

.075 g. of fl-hydroxynaphthoic anilide, .080 g. of4-benzamido-2,5-diethoxy-aniline and .200 g. of guanidine carbonate weredissolved in 1 cc. of Cellosolve and cc. of caustic soda (40 B.). Thiswas diluted with 150 cc. of warm water containing .10 g. of Talmol NNO.

10 g. of nylon yarn were dyed and developed as above. Onspectrophotometric test, 71.8% of the B-hydroxy-naphthoic acid anilidewas taken up by the fiber and only 28.2% remained in the dyebath incontrast to the above figures of 43.7% and 56.3% respectively.

Also the yarn dyed in the presence of the guanidine carbonate was muchbrighter and darker than in the case where the guanidine carbonate wasmissing.

The p-hydroxynaphthoic acid-m-nitroanilide exhausted to about 60%without and 93% with guanidine carbonate. Accordingly 64 parts of suchamide plus guanidine carbonate should at least equal 100 parts of theamide without guanidine carbonate.

Accordingly the following baths were prepared (amounts are in grams,unless otherwise specified):

10 g. skeins of nylon yarn were impregnated in the respective baths for45 min. at 60 C., then rinsed in fresh water and developed in a bath for45 min. at 35 C. containing 3 g. of 2-methoxy-4- anilinoanilinediazonium sulfate, .3 cc. of Diazopon A (commercial surface activeagent) and 300 cc. of water. The yarn was soaped at the boil for 5 min.,rinsed and dried.

Dyeing from bath II (the control) is extremely strong and bright. Dyeingfrom bath III is considerably stronger than that from bath I. Accordingto calculations, the same amounts of B- hydroxynaphthoicacid-m-nitroanilide should be absorbed from baths I and III. In bath IV,half the amount of such anilide was used as in bath III but IV stillexhibits a stronger and brighter dyeing than I. This means that theguanidine carbonate exerts an extremely beneficial action.

Example XLII The following two baths were prepared (quantities in gramsunless otherwise specified) I II 5-chlore-2,4-dimethoxyacetoacetanilide250 250 guanidine carbonate 300 Oellosolve c. V4 caustic soda, 40 BL 34warm Water cc 150 150 fi-rnethyl-o-anisidine... 110 oleyl methyl tauride010 010 Cellosolve I .cc. $4 ,-4

The 5-chloro-2,4-dimethoxyacetoacetanilide, uanidine carbonate,Cellosolve and caustic soda were combined and diluted with the Water.The mixture containing the 5-methyl-o-anisidine, oleyl methyl taurideand Cellosolve was added. 10 g. samples of nylon yarn were dyed at 60 C.for 45 min., rinsed and developed with 5% (based on the weight ofmaterial) of sodium nitrite and 10% acetic acid in 300 cc. of water for30 min. at 60 C. The dyeings were then finished as usual.

The dyeing from bath I which contained no guanidine carbonate is a dullorange yellow whereas the dyeing made in the presence of guanidinecarbonate is a very bright strong greenish-yellow shade.

I claim:

1. In the process of dyeing nylon on the fiber by impregnating thefibers with an amine base and a Naphthol AS coupling componentsimultaneously and subsequently diazotizing the base and coupling thediazo with the coupling component, the improvement which compriseseffecting the impregnation of the fibers with said coupling component inthe present of an amount of a uanidine compound at least molecularlyequivalent to the Naphthol AS but within the limits of 1% to 5% byweight of the fibers to be dyed, said guanidine compound selected fromthe class consisting of those of the following formulae:

wherein R1 and R2 are selected from the class consisting of hydrogen,alkyl, aryl, aralkyl and cycloalkyl, and the salts of such compounds.

2. The process as defined in claim 1 wherein the fibers are impregnatedin the presence of the guanidine compound with an aqueous solution ofthe amine base and the coupling component.

3. The process as defined in claim 1 wherein the fibers are impregnatedwith an aqueous solution of a salt of the ice color coupling componentand guanidine compound and the amine base.

4. The process of dyeing nylon on the fiber with an ice color whichcomprises impregnating the fibers with an amine base and a Naphthol AScoupling component simultaneously present in an aqueous solutioncontaining an amount of guanidine carbonate at least molecularlyequivalent to the Naphthol AS but within the limits of 1% to 5% byweight of the fibers to be dyed, effecting the diazotization of theamine base and 15 coupling the diazo compound thereby resulting with thecoupling component.

5.' In the process of dyeing acetate rayon on the fiber by impregnatingthe fibers with an amine base and a Naphthol AS coupling componentsimultaneously and subsequently diazotizing the base and'couplingthe'diazo with the coupling component, the improvement whichcomprises efiecting the impregnation of the fibers with said couplingcomponent in the presence of an amount of a guanidine compound at leastmolecularly equivalent to the Naphthol AS but within the limits of 1% toby weight of the fibers to be dyed, said guanidine compound selectedfrom the class consisting of those of the following formulae:

wherein R1 and R2 are selected from the class consisting of hydrogen,alkyl, aryl, aralkyl and cycloalkyl, and the salts of' such compounds.

6. The process as defined in claim 5 wherein the fibers are impregnatedin the presence of the guanidine compound with an aqueous solution ofthe amine base and the coupling component.

1 6 7. The process asrdefined in. claim 5 wherein the fibers areimpregnatedwith an aqueous solution of a salt: of the" couplingcomponent and guanidine compoundand' the amine base.

8. The processoft dyeingacetate rayon on the fiber with an ice colorwhich comprises impregnating the fibers with an amine base and aNaphthol AS-coupling'component simultaneously present in an aqueoussolution containing an amount of guanidine carbonate at leastmolecularly equivalent to the Naphthol AS but within the limits of 1% to5% by weight of the fibers to be dyed, efi'ecting the diazotization ofthe amine base and coupling the diazo compound thereby resulting withcoupling component.

CLEMENS STRECK.

References-Cited in the file of this patent UNITED STATES PATENTS NumberName Date 1,822,548 Ter. Horst- Sept. 8, 1931 1,963,974 Ellis June 26,1934- 2,190,746 Von Glahn Feb. 20, 1940 2,304,821 Hansenet a1; Dec. 15,1942 2,367,534 Smith et a1 Jan. 16, 1945 2,385,719 Migrdichian Sept. 25,1945 FOREIGN PATENTS Number Country Date 502,861 Great Britain Mar. 22,1939 486,696 Germany Nov. 23, 1929 348,269 Great Britain May 14, 1931643,323 France-. l May 15, 1928

1. IN THE PROCESS OF DYEING NYLON ON THE FIBER BY IMPREGNATING THEFIBERS WITH AN AMINE BASE AND A NAPHTHOL AS COUPLING COMPONENTSIMULTANEOUSLY AND SUBSEQUENTLY DIAZOTIZING THE BASE AND COUPLING THEDIAZO WITH THE COUPLING COMPONENT, THE IMPROVEMENT WHICH COMPRISESEFFECTING THE IMPREGNATION OF THE FIBERS WITH SAID COUPLING COMPONENT INTHE PRESENT OF AN AMOUNT OF A GUANIDINE COMPOUND AT LEAST MOLECULARLYEQUIVALENT TO THE NAPHTHOL AS BUT WITHIN THE LIMITS OF 1% TO 5% BYWEIGHT OF THE FIBERS TO BE DYED, SAID GUANIDINE COMPOUND SELECTED FROMTHE CLASS CONSISTING OF THOSE OF THE FOLLOWING FORMULAE:
 2. THE PROCESSAS DEFINED IN CLAIM 1 WHEREIN THE FIBERS ARE IMPREGNATED IN THE PRESENCEOF THE GUANIDINE COMPOUND WITH AN AQUEOUS SOLUTION OF THE AMINE BASE ANDTHE COUPLING COMPONENT.